Wash agents



United States Patent 3,413,221 7 WASH AGENTS Ernst Gotte,Dusseldorf-berkassel, Werner Stein, Dusseldorf-Holthausen, and HerbertWeiss, Cologne-Deutz, Germany, assignors to Henkel & Cie, G.m.b.H.,Dusseldorf-Holthausen, Germany, a corporation of Germany No Drawing.Continuation of application Ser. No. 171,283, Feb. 5, 1962. Thisapplication July 28,

1966, Ser. No. 568,677 Claims priority, appligtlltion Germany, Mar. 1,1961,

14 Claims. (ci. 252-138) ABSTRACT OF THE DISCLOSURE foam improvementagents, wash alkalis, anhydrous phosphates, perborate, stabilizertherefor, weak acid reacting compounds, and/ or soil removing agents.

This application is a continuation of application Ser. No. 171,283,filed Feb. 5, 1962, now abandoned.

This invention relates to improved wash agent compositions, and moreparticularly it relates to improved wash agent compositions comprisingsynergistic mixtures of sulfonated salts of saturated fatty acid esters,sulfated fatty alcohols and/or alkyl benzene sulfonates.

Dialkyl salts of sulfonated fatty acids alone and 1n combination withalkali alkylbenzene sulfonates and/or alkali salts of sulfated fattyalcohols have already been evaluated with respect to their effectivenessas wash agents. The salts of sulfonated fatty acids alone, the salts ofalkyl benzene sulfonates, and the salts of the fatty acids alone havebeen found not to be entirely satisfactory due to their limitedsolubility at operating temperatures, the ultimate expense to theconsumer, their effectiveness as dirt removal agents, etc. In certaininstances as, for example, in the case of the combination of long chainalkyl sulfates and alkali salts of sulfonated fatty acids, the mixturehas been found to be characterized by synergism.

One of the objects of the invention is the provision of a novel washingagent composition of the type indicated possessing superior properties,making it especially advantageous for use in various laundryapplications.

Another object of the invention is the provision of wash-agentcompositions which are adapted for use either as fine or boilingwash-agents and which are superior to the wash-agents of the samegeneral type now available.

Another object of the invention is to provide improved wash-agentcompositions based on mixtures of sulfonated salts of saturated fattyacid esters, sulfated fatty alcohol and/ or alkyl benzene sulfonates.

Other objects will appear hereinafter.

In accordance with the invention, it has been found that wash-agentshaving superior properties are obtained by combining a sulfonated saltof a saturated fatty acid ester with a sulfated fatty alcohol and/or analkyl benzene sulfonate.

The alkyl benzene sulfonates in accordance with the invention arepreferably selected so that the alkyl radical contains chain branchings,as a result of which the same are much more slowly decomposed bybacteria in the Birth-Lite;

b.- er.

Patented Nov. 26, 1968 liquid washing medium than are alkyl benzenesulfonates characterized by straight alkyl chains. The alkyl benzenesulfonates, in accordance with the invention, are generally produced bypolymerizing propylene, condensing a polypropylene with benzene toobtain the alkyl benzene, and thereafter sulfonating the alkyl benzene.The polypropylene benzene sulfonates having 9-15 carbon atoms in thealkyl radical and in particular having 12 carbon atoms in the alkylradical have proved especially effective. Generally, at least of thealkyl benzene molecules present in an isomeric mixture possess 12 carbonatoms in'the alkyl radical, and these alkyl benzene sulfonates have cometo be called by the term tetrapropylene benzene sulfonate. However, inaccordance with the invention, it has been established that, in additionto tetra-propylene benzene sulfonate, alkyl benzene sulfonates, thealkyl component of which exhibits other branchings or alkyl benzenesulfonates the alkyl component of which is of an unbranched nature-i.e.,straight chainmay also be satisfactorily used in the compositions of theinvention.

The sulfated fatty alcohols used in the present invention are obtainablefrom saturated or unsaturated, and preferably straight chain fattyalcohols, having l020 and preferably 12-18 carbon atoms in theirmolecule.

The sulfonated fatty acid ester salts for use in the compositions of theinvention are obtained in the known manner, either by the introductionof the sulfonic acid group into the fatty acid radical, followed byesterification of the carboxylic group by means of a monovalent alcohol,or, alternatively, by introducing the sulfonic acid radical into anester obtained by esterifying a fatty acid by means of a monovalentalcohol. Both of these alternative processes produce esters of sulfonicfatty acids The fatty acids which may be.used are preferably saturatedstraight chain fatty acids having l0-20, and preferably 12-18, carbonatoms, and the alcohol radical is preferably derived from a monovalentstraight chain saturated aliphatic alcohol having 1-10 carbon atoms inits molecule. The starting fatty acid and alcohol are selected with aview that the ester product produced contains at least 11 and, at most,22 carbon atoms, preferably 13-20 carbon atoms.

The various esters falling within the aforesaid definition are allwater-soluble but to different degrees; their solubility decreasing withan increase in the number of carbon atoms present in the molecule. Inaddition, the washing and the foaming properties of the sulfonated estersalt are dependent on the molecular size. Generally, the generalstatement may be made that the more readily soluble compounds, i.e.,those having a smaller number of carbon atoms, are characterized by abetter foaming capacity, while the other ester salts having the largernumber of carbon atoms are capable of effecting a better washing.However, the washing and foaming capabilities of the sulfonated estersalts in addition are dependent on the structure of the compound, andspecifically the combination of fatty acid and fatty alcohol employed inthe esterification, the other materials which are present in the washingmedium and, for example, those contributing to the hardness or softnessof the water as well as on the temperature of the washing medium. Whilethe more readily soluble sulfonated ester salts are equally suitable foruse at room temperature or at slightly increased temperatures as, forexample, up to about 50 C., the less readily soluble sulfonated estersalts are advantageously used only at higher temperatures of aboutS0-l00 C. It is, therefore, advisable in selecting a sulfonated estersalt salt for the combination to suit the compound selected for itsintended use.

The sulfonated ester salts of fatty acids having 12-14 carbon atoms andalcohols having 1-4 carbon atoms have been found to be particularly goodfoam-producing agents while'the sulfonated ester salts of fatty acidshaving 16- 18 carbon atoms and alcohols having 1-4 carbon atoms, thetotal number of carbon atoms present in the ester molecule not exceeding20, demonstrate especially good washing properties. Between the twogroups of sulfonated ester salts as above set out are to be found thecompounds having foaming and washing properties intermediate those ofthe two groups and in certain instances as, for example, the sulfonatedester salts of palmitic acid esters of alcohols having 2-4 carbon atomsin the molecule which constitute good foaming as well as good washingagents.

In the preparation of the sulfonated ester salts in accordance with theinvention, the fatty acids are generally of natural origin and, in theproduction of the sulfonated ester salt, the starting fat material isselected on the basis that its fatty acid composition will come closestto that which is required for producing the desired properties in thefinal sulfonated salt ester.

In preparing sulfonated ester salts characterized by good foamingproperties, the fat starting materials which are selected are thosewhose fatty acid components in the main consist of fatty acids having12-14 carbon atoms. This fat starting material includes the so-calledlauric acid fats" by which is intended the group of fats so termed andfurther defined in A. E. Bailey: Industrial Oil and Fat Products, NewYork, 1951, page 121. The most important fats and those of greatestpractical significance coming within this definition are enumerated byBailey at pages 133-138 of the aforesaid publication. In the productionof sulfonated ester salts having good washing properties, there may beemployed the other natural fats and/or their hydrogenation products,which preferably contain 16-18 carbon atoms. It has been found that theesters of hydrogenated tallow fatty acids are particularly favorablestarting materials in this connection.

According to the invention, the combinations are optimally effectivewhen the sulfonated ester component is present in an amount of from20-90 weight percent of the total synthetic wash-active material, thealkyl benzene sulfonate and/or sulfated fatty alcohol constituting theremainder. The alkyl benzene sulfonate and sulfated fatty alcohol may bepresent in any desired mixing ratio. Preferably, the sulfonated estersalt is present in an amount of from 35-70 weight percent referred tothe combination washing agent.

In many instances, the composition producing optimal effect as regardswashing capacity for a specific combination of wash-active substances isalso capable of producing the optimal foaming capacity. Suchcombinations are then advantageously employed in the production of afoaming wash-agent. The foaming quality of such agents may be furtherimproved through the addition of any of the known foaming stabilizers tothe composition.

In other combinations, the optimal ranges for superior washing andfoaming qualities do not coincide and in such instances as, for example,in the cases of agents characterized by good washing and mediocre topoor foaming properties, the combinations are suitable for theproduction of low foaming preparations and are particularlyadvantageously used in washing machines.

A particular advantage and desirable characteristic of the wash-activecombinations, in accordance with the invention, are to be found in thefact that the sulfonated ester salts and the sulfated fatty alcohols sofar as they are derived from straight-chain fatty alcohols, are excellently biologically exhausted-i.e., destroyed-in water. As a result, thedanger of froth or foam formation on the waste water is substantiallyeliminated even in con= nection with the use of the combinations of theinvention,

which additionally contain the alkyl benzene sulfonates ortetrapropylene benzene sulfonates, both of which are not readilydecomposed. The foaming property of the waste water remaining after thewashing treatment is therefore not only diminished in that theconcentration of the total wash-active substances becomes less with theexhaustion of the sulfonated ester salt but also in that the combinationis taken out of the range of optimal composition for improved foamingcapacity by the destruction of the sulfonated ester salt which has takenplace.

The wash-agent combinations in accordance with the invention aresuitable for use per se or in admixture with the conventional productsemployed in the formulation of wash-agents for use in the washing andbleaching treatment of textiles, and which impart to the preparation. asdetermined by its intended use, a pH value within the range of 6-12. ThepH value is determined using as the test sample a 1% solution of awash-agent. The pH range extending from 6-12 includes the agentsintended as fine wash-agents and which are required to be regulated soas to have a slightly acid to alkaline pHi.e., approximately within therange of 68.5, and preferably within the range of 7-8, as well as theagents intended for use as boiling wash-agents and having a pH valueapproximately within the range of 9-12 and preferably of from 9.5-1L5.

The wash-agents in accordance with the invention may be employed inconjunction with neutral or alkaline reacting salts, slightly acidreacting compounds, as well as the customary agents used to improvefoaming, soil removal, and such additives as bleaching agents, corrosionprotection agents, etc.

A neutral reacting salt which is most advantageously used is sodiumsulfate, the same additionally acting to improve the effectiveness ofthe combination in accordance with the invention.

The wash-alkalies which are suitable for use in connection with theinvention include the alkali carbonates, alkali-bicarbonates,water-soluble alkali silicates, alkaliorthophosphates, etc.

The combination wash-agent in accordance with the invention may be usedto particular advantage in conjunction with the anhydrous phosphates.The anhydrous phosphates employed may be any polyphosphate, such as, apyrophosphate or metaphosphate, the tripolyphosphates andtetrapolyphosphates having been found to possess particular practicalsignificance. The pyroand polyphosphates are alkaline in reaction andare therefore able, when used alone in boiling wash-agents, to impart tothe same the necessary alkalinity. However, the metaphosphates produce aslightly acid reaction and are therefore advantageously utilized in theproduction of fine wash-agents serving to decrease the pH value of theresulting combination. Examples of other phosphates suitable for thesame purpose include the acid orthophosphates and the acidpyrophosphates. Weak inorganic or organic acids or acid salts of stronginorganic acids, such as, for example, boric acid, citric acid, oxalicacid, lactic acid, glycolic acid, tartaric acid, and amido-sulfonicacid, are instances of other materials suitable for use in regulatingthe pH value of the washing agent.

Still further, the preparation in accordance with the invention may beused in combination with the other ordinary substances as are used inwash-agents. These substances include inorganic or organic active oxygencarriers, as, for example, the percompounds and, in particular, sodiumperborate. Products functioning to improve the soil removal property andfoaming qualities of the combination wash-agent are additionallyincluded in the preparation of the wash-agent. Instances of substancesserving to improve the soil removal capacity of the wash-agent includewater-soluble colloids, and preferably those of an organic nature, as,for example, the water-soluble salts of polymeric carbon acids, sizes,gelatin, salts of ether carbon acids or ether sulfonic acids of starchor cellulose, or salts of acid sulfuric acid esters of cellulose orstarch. Additives for improving the foaming capacity of the wash-agentcombination of the invention include fatty acid amides which may besubstituted at the nitrogen atom with alkylor alkylol-radicals having atmost 6 carbon atoms per radical, as well as the addition products ofethylene oxide to these unsubstituted or substituted fatty acid amides.

The salts which may be added to the wash-agents in accordance with theinvention may be derived from inorganic or organic alkalies as, forexample, from sodium, potassium or fiom the easily soluble organicamines. Such salts include alkylol amines, for example, mono, di, ortriethanolamine. The easily soluble salts which may be used inconjunction with the wash-agent combination of the invention includewash-active organic sulfates or sulfonates, such additions beingparticularly valuable in the production of the wash-agents to be used inpaste or liquid form.

It can be appreciated that it is generally desirable in compoundingwash-agent preparations so that, in s;ite of the high concentration ofactive material, they do not form precipitates readily. To this end itis advisable to use, in connection with the additions, anions which arealready present in the wash-agent, although similar thought has to begiven to the anionic wash-active additives as they are advantageouslyadded in the form of their readily soluble salts with inorganic ororganic cations. It is, therefore, advisable to provide, in manyinstances, for the presence of various cations in the washingcombination, paving the way for satisfactory further additions.

It has been found advantageous to include in the final preparationscertain solving agents as exemplified by the hydrotropic materials ofthe type of toluene or' xylene sulfonates and, in addition,water-soluble organic solvents. The water-soluble organic solvents whichare particularly suitable are those having boiling points above 100 C.,such as, for example, the ethers or polyethers of polyvalent alcoholsand the partial ethers of polyvalent and monovalent alcohols. Instancesof suitable solvents include tri-, tetraor polyethyleneglycol,polyglycerins, the partial ethers of ethyleneglycol, propyleneglycol,glycerin, and aliphatic monovalent alcohols having 1-4 carbon atoms.

The wash-agents, in accordance with the invention, as has already beennoted, are suitable for use alone or in combination with variousadditives, instances of which have been set forth. Additionally, theagents or the compositions containing the same as active ingredients,can be employed in the solid form (powder or lumps), as pastes or creamsor in the form of their solutions.

In order to enable those skilled in the art to even more fullyappreciate the nature of the invention, the following examples are givenas illustrative of specific embodiments of the invention. It will beunderstood that they are given by way of example only, in order thatthose skilled in the art will have a clearer picture of how theinvention may be successfully practiced, and are not to. be construed aslimiting the invention in any way. Thus, for example, the proportions ofthe components, the temperature of the washing medium, the additions,etc., and other conditions, may be varied without departing from thescope of the invention as defined in the appended claims.

The results described in the examples were obtained in laboratory testsin which the wash-active combinations, in accordance with theinvention-the components being present as sodium salts-were studiedusing two different kinds of laundry as test matteri.e., thatconventionally designated fine laundry and a more heavily soiled cottonlaundry conventionally designated boiling laundry. These two types oflaundry present different soil removal problems and wash-active agentseffective with one are not necessarily effective with the other. In thefine laundry tests, wool soiled with a skin secretion was washedemploying therefor a bath ratio of 1:40.

Further conditions employed in the laundering tests are set forth asrequired in the examples. In connection with such conditions, there arenoted, for the same, in the examples, those combinations of thewash-active substances which under such established conditions arepossessed of good washing activity (cleaning properties) and/or goodfoamingproperties-that is, in which the eflect reported was at least asgreat but preferably greater, i.e., over that of the effect alone of themost important component of the wash-active combination and the optimalrange within which a clearly synergistic effect could be recognized and,specifically, in which the effect of the combination considerablyexceeded the sum of the individual components effects. In consideringthe ranges of a good or optimal effect, as indicated in the examples, itmust be taken into account that the same are to a degree dependent onthe conditions of use of the wash-agents as, for example, on theconcentration, degree of water hardness, further constituents of thewash-agent, etc.

The tests were carried out using as wash-agents, agents in which thewash-active substance was only present in combination with sodiumsulfate, in order that the effect of the wash-active substance as far aspossible be unaffected by the effect of any of the other possiblewashagent additions.

By the term wash-agent there is intended the technical more or less purewash-active substance combinations which, as a result of theirmanufacture, still contain slight amounts of sodium sulfate as well asthe products which have been processed to completion, as, for example,by addition thereto of the conventional wash-agent additions and whichqualify as fine or boiling wash-agents. In the case of the fine washagents, sodium sulfate may be present in large quantities since the sameconsists in the effect of the wash-active substance or substances. Incertain instances the washing effect of the fine wash-agent can beincreased by replacing the sodium sulfate by magnesium sulfate andparticularly if the magnesium sulfate which is added is not brought intoprecipitation by the other wash-agent components.

The wash-agents in accordance with the invention have approximately thefollowing composition:

5-75 weight percent and preferably 10-35 weight percent of a wash-activecombination in accordance with the invention;

0-20 weight percent and preferably 1-5 weight percent of a foamstabilizer; the same must not however amount to more than 50 weightpercent referred to the total amount of synthetic anionic wash-activesubstances of the sulfate or sulfonate-type present;

0-70 weight percent and preferably 10-50 weight percent of wash alkalis;

0-70 weight percent and preferably 5-40 weight percent of anhydrousphosphates;

0-3.5 weight percent and preferably 0-3 weight percent of an activeoxygen material present as any of the conventional active oxygencarriers as, for example, a percompound;

0-15 weight percent and prefarbly 3-10 weight percent of a sabilizer forthe active oxygen compound;

0-20 weight percent and preferably 0-10 weight percent of a slightlyacid reacting compound;

0-2 weight percent and preferably 0.2-1.5 weight percent of an additiveor additives serving as soil removal agents.

It is, of course, to be understood that the wash-active combinations ofthe invention may be used in other concentrations and proportions thanare indicated in the examples and that it is not intended to limit theinvention to those values as set out in the examples. Preferably, the

7 range of concentration of the wash-active combination lies beween 0.3-g./l. and most preferably within the range of 0.5-2 g./l.

Example 1 Wash-agent composition:

33 weight percent of a mixture of tetrapropylene benzene sulfonate and asulfonated palmitic acid ethyl ester salt;

67 weight percent Na SO Conditions of use:

1 g./l. agent in water of German hardness and having a temperature of 40C.

Good or optimal foaming capacity at:

30-70 (40-60) weight percent sulfonated fatty acid acid ester salt.

Example 2 A wash-agent of the type as set out in Example 1 and under theworking conditions therein indicated is utilized with good or optimalwashing capacity it the sulfonated palmitic acid ethyl ester salt isreplaced by the following sulfonated ester salts:

-90 (20-50) weight percent of the sulfonated ester salt of palmitic acidmethyl ester; 20-90 (-90) weight percent of the sulfonated ester salt ofpalmitic acid isopropyl ester; 40-90 weight percent of the sulfonatedester salt of palmltic acid butyl ester;

20-95 (30-90) weight percent of the sulfonated ester salt of stearicacid ethyl ester;

-95 (-90) weight percent of the sulfonated ester salt of stearic acidisopropyl ester.

Example 3 Wash-agent composition:

30 weight percent of a mixture of a sulfated C -C fatty alcohol and asulfonated palmitic acid butyl ester salt;

70 weight percent Na SO Conditions of use:

1 g./l. of wash-agent in water having 20 German hardness and atemperature of 40 C. Good or optimal washing capacity:

20-90 (30-80) weight percent of sulfonated ester salt.

Example 4 Wash-agent composition:

24 weight percent of a mixture of tetrapropylene benzene sulfonate, asulfated C -C fatty alcohol, and the sulfonated ester salt of ahydrogenated palm kernel fatty acid isopropyl ester;

42.6 weight percent Na P O 6.7 weight percent Na O.3.3SiO

26.7 weight percent Na SO Conditions of use:

1 g./l. wash-agent in permuted water having a temperature of 40 C.

Optimal foaming properties using as source of soiling of the cloth askin secretion:

10-30 (15-25) weight percent of sulfonated ester salt;

65-45 (60-50) weight percent of fatty alcohol sulfate:

15-45 (25-35) weight percent of tetrapropylene benzene sulfonate.

Example 6 Wash-agent composition:

20 weight percent of a mixture of a sulfated C -C fatty alcohol and thesulfonated ester salts of the methyl esters of a hydrogenatedtallow-fatty acid and a hydrogenated palm kernel fatty acid;

weight percent Na SO Conditions of use:

1.5 g./l. of wash-agent in water having a 10 German hardness and atemperature of 40 C. Good or optimal washing capacity:

8-43 (18-27) weight percent of fatty alcohol sulfate;

57-92 (73-82) weight percent of the sulfonated ester salt ofhydrogenated tallow fatty acid methyl ester;

0-16 (0-2 weight percent of the sulfonated ester salt of hydrogenatedpalm kernel fatty acid methyl ester.

Good or optimal foaming capacity:

13-l9 (17) weight percent of fatty alcohol sulfate; 20-57 (31-33) weightpercent of sulfonated ester salt of hydrogenated tallow fatty acidmethylester; 38-67 (49-51) weight percent of sulfonated ester salt ofhydrogenated palm kernel fatty acid methylester.

As the ranges in which good or optimal foaming capacity are obtained donot overlap in this example of wash-active combination, it isadvantageously applied in the production of wash-agents characterized bylow foaming capacity.

Example 7 Wash-agent composition:

20 weight percent of a mixture of a sulfated C -C fatty alcohol and thesulfonated ester salts of the hydrogenated ethylesters of a tallow fattyacid and a palm kernel fatty acid;

80 weight percent Na SO Conditions of use:

1.5 g./l. of wash-agent in water having a 10 German hardness and atemperature of 40 C. Good or optimal washing capacity:

5-51 (5-48) weight percent fatty alcohol sulfate;

45-88 (52-85) weight percent of the sulfonated ester salt ofhydrogenated tallow fatty acid ethylester;

0-45 (0-25) weight percent of the sulfonated ester salt of hydrogenatedpalm kernel fatty acid ethylester.

Within the range which has been indicated for optimal washing capacity,the optimal foaming capacity is to be found in the followingcompositions:

15-25 weight percent fatty alcohol sulfate; 55-65 weight percentsulfonated ester salt of hydrogenated tallow fatty acid ethylester;15-25 weight percent sulfonated ester salt of hydrogenated palm kernelfatty acid ethylester.

Example 8 Wash-agent composition:

30 weight percent of a mixture of tetrapropylene benzene sulfonate, asulfated G -C fatty alcohol and equal parts by weight of q-sulfonic acidsalts of hydrogenated tallow fatty acid ethylester and of hydrogenatedpalm kernel fatty acid ethylester;

70 weight percent Na SO Conditions of use:

1.5 g./l. of wash-agent in water having a 10 German hardness and atemperature of 40 C. Good or optimal. washing and foaming capacity:

9 37-80 (43-62) weight percent tetrapropylene benzene sulfonate; -38(0-27) weight percent fatty alcohol sulfate; 15-54 (28-40) weightpercent sulfonated ester salt.

Example 9 The foaming properties of two wash-agents having the followinggeneral composition were determined according to the procedurehereinafter set out:

The remainder consisting of sodium sulfate and water.

Normally soiled household laundry was washed for 15 minutes in arotating vane-type of laundry machine employing, as washing medium, abath having a concentration of 4 g./l. of wash-agent in water having 16German hardness and which had been heated to a temperature of 90 C. Ineach run 4 liters of the washing medium which had been used in the runwere removed following completion of the washing. The used washingmedium withdrawn at a temperature of 80, 60, 40, and 25 C.,respectively, was permitted to flow from a vessel having an outlet of3.25 mm. clear width within 4 minutes from a height of 80 cm. into acylindrical vessel having a diameter of 21.5 cm. The quantity of foamwhich was formed as a result in the collecting vessel was measuredimmediately, and at subsequent intervals of 1, 3, 4, 5, and 10 minutesand the heights of the foam recorded in each instance added together.The sum thereby obtained constitutes a good gauge for the foamingproperties of the solution being measured under conditions closelyparalleling those in actual practice. It takes into consideration theinitial foaming capacity as well as the foam stability. The two washingagents which were tested both contained 20 weight percent of wash-activesubstance, in one instance, the wash-agent consisted of 16 weightpercent .tetrapropylene benzene sulfonate and 4 weight percent of asulfated C t-C fatty alcohol, while, in the other instance, thetetrapropylene benzene sulfonate had been replaced by one-half by asulfonated hydrogenated palm kernel fatty acid methylester. The latterwashing agent was superior in the foaming properties observed to theagent which contained only the tetrapropylene benzene sulfate.

Example 10 Wash-agent composition:

30 weight percent of a mixture of a sulfated C -C fatty alcohol and thesulfonated ester salt of the ethylester of a hydrogenated palm kernelfatty acid; 50 weight percent Na SO 20 weight percent Na P- .O-,.Conditions of use:

1.5 g./l. of wash-agent in water having a 10 German hardness and atemperature of 40 C. Good optimal washing capacity:

23-90 (40-80) weight percent of sulfonated ester 1.. As the sulfonatedester salt used herein displays an excellent foaming behavior, a good oroptimal foaming capacity is limited to the comparatively narrow range of2 390 (60-70) weight percent of sulfonated ester Example 11 Wash-agentcomposition:

30 weight percent of a mixture of a sulfated C -C fatty alcohol and thesulfonated ester salt of the ethyl ester of a hydrogenated tallow fattyacid; 50 weight percent Na,so,-,

20 weight percent Na P O Conditions of use:

1.5 g./l. wash-agent in water having a 10 German hardness and atemperature of 40 C. Good or optimal washing and foaming capacity:

30-90 (40-60) weight percent of sulfonated ester salt.

Example 12 Wash-agent composition:

30 weight percent of a mixture of a sulfonated ester salt of ahydrogenated palm kernel fatty acid ethyl ester with an alkyl benzenesulfonate, the alkyl COmPOl'lCjli of which is substantially unbranchedand which may be, for example, derived by carbonmonoxide hydrogenationof a C -C hydrocarbon fraction, followed by chlorination, condensationwith benzene, and sulfonation of the alkyl benzene, or, alternatively,by condensing a corresponding fraction of an essentially straight-chainolefin, obtained from a natural source, condensing the same withbenzene, and sulfonating the alkyl benzene condensation product. Alkylbenzene sulfonates thus produced are characterized by a content ofcompounds having 12 and 13 carbon atoms in the alkyl radical of morethan 50%. 70 weight percent sodium sulfate.

Conditions of use:

1.5 g./l. wash-agent in water of 10 German hardness and having atemperature of 40 C.

Good or optimal washing capacity:

10-60 (25-35) weight percent sulfonated fatty acid ester salt;

Good or optimal foaming capacity:

20-90 (45-55) weight percent sulfonated fatty acid ester salt.

Example 13 Wash-agent composition:

30 weight percent of a mixture of the sulfonated ester salt of ahydrogenated tallow fatty acid ethyl ester with an alkyl benzenesulfonate as described iri Example 12.

70 weight percent of sodium sulfate.

Conditions of use:

1.5 g./l. wash-agent in water of 10 German hardness and having atemperature of 40 C.

Good or optimal washing capacity:

20-90 (45-55) weight percent ester salt;

Good or optimal foaming capacity:

5-25 (10) weight percent sulfonated fatty acid ester salt.

What is claimed is:

1. A washzagent consisting essentially of:

(1) as first component, about 20-90 weight percent of a sulfonated fattyacid ester salt constituting the salt of an'ester of a saturated fattyacid having from 10-20 carbon atoms and a saturated monovalent aliphaticalcohol having 1-10 carbon atoms, c0ntain ing the sulfonic acid group inthe fatty acid radical and having the formula SOs wherein R-CH-COOdesignates the fatty radical and R the monovalent aliphatic alcoholradical, and

(2) as second component, about -10 weight percent of at least one memberselected from the group consisting of sulfated fatty alcohols having10-20 carbon atoms in the alkyl radical and alkyl benzene sulfonateshaving 9-15 carbon atoms.

2. A wash agent according to claim 1 additionally containing sodiumsulfate up to 80 percent of the total mixture.

3. A wash agent according to claim 1, wherein said sulfonated fatty acidsulfonated ester salt is present in an amount of between about 35 and 70weight percent based on the weight of the sulfonated ester salt togetherwith said second component.

4. A wash agent according to claim 1, the 1 percent aqueous solution ofwhich has a pH of 6-12.

5. A wash agent according to claim 1, wherein the total number of carbonatoms in said sulfonated ester salt does not exceed 20.

6. A wash agent according to claim 1, wherein said sulfonated ester salthas 13-20 carbon atoms.

7. A .wash agent according to claim 1, wherein said alkyl benzenesulfonate is tetrapropylene benzene sulfonate and said sulfated fattyalcohol has 12-18 carbon atoms.

8. A wash agent according to claim 1, wherein said sulfonated ester saltconstitutes the esterification product of a saturated fatty acid derivedfrom the lauric acid fat group with a staturated monovalent aliphaticalcohol having 1-4 carbon atoms.

9. A wash agent according to claim 1 having improved foaming propertiesin which said sulfonated fatty acid ester salt constitutes the salt ofan ester of a saturated fatty acid having from 12-14 carbon atoms and asaturated monovalent aliphatic alcohol having 1-4 carbon atoms.

10. A wash agent according to claim 1 having improved washing propertiesand a low foaming capacity in which said sulfonated fatty acid estersalt constitutes the salt of an ester of a saturated fatty acid havingfrom 16- 18 carbon atoms and a saturated monovalent aliphatic alcoholhaving l-4 carbon atoms.

11. A wash agent according to claim 1 containing 33 weight percent of amixture of tetrapropylene benzene sulfonate and a sulfonated palmiticacid ethyl ester salt', and

67 weight percent of sodium sulfate.

12. A wash according to claim 1 containing 30 weight percent of amixture of a sulfated cur-C fatty alcohol and a sulfonated palmitic acidbutyl ester salt; and

70 weight percent sodium sulfate.

13. A wash agent according to claim 1 containing 30 weight percent of amixture of tetrapropylene benzene sulfonate, a sulfated C -C fattyalcohol, and a sulfonated ester salt of palmitic acid butyl ester; and

70 weight percent of sodium sulfate.

14. A wash agent according to claim 1 in the form of a mixture in whichsaid first and second components together constitute (a) -75 weightpercent thereof with 12 the remainder of (b) 25-95 weight percent beingcomposed of (i) 0-20 weight percent of a foam improving agent selectedfrom the group consisting of fatty acid amides and their additionproducts with ethylene oxide,

(ii) 0-70 weight percent of a wash alkali selected from the groupconsisting of alkali metal carbonates, alkali metal bicarbonates, andalkali metal silicates,

(iii) 0-70 weight percent of an anhydrous alkali metal phosphateselected from the group consisting of ortho phosphates, andpolyphosphates,

(iv) 03.5 weight percent of an alkali metal perborate compoundconstituting an active oxygen carrier, (v) 0-15 weight percent of MgSiO,as stabilizer for said active oxygen carrier compound,

(vi) 0-20 weight percent of a weak acid reacting compound selected fromthe group consisting of'boric acid, citric acid, oxalic acid, lacticacid, glycolic acid, tartaric acid, amido-sulfonic acid, and acid saltsof strong inorganic acids, and

(vii) 0-2 weight percent of a soil removing agent selected from thegroup consisting of water-soluble sizes, gelatin, salts of ethercarboxylic acids of cellulose, salts of ether carboxylic acids ofstarch, salts of ether sulfonic acids of cellulose, salts of ethersulfonic acids of starch, salts of acid sulfuric acid esters ofcellulose and salts of acid sulfuric acid esters of starch.

References Cited UNITED STATES PATENTS 2,043,476 6/1936 Guenther et al.260-400 2,303,212 11/1942 Kjse et al 252-121 2,460,968 2/1949 Bert etal. 260400 2,806,044 9/1957 Weil et al. 260-400 2,876,200 3/1959 Strainet al 252-99 X 2,972,583 2/1961 Hewitt 252-152 X 3,338,838 8/1967 Wilson252-161 OTHER REFERENCES Stirton et al., Surface Active Properties ofSalts of Alpha-Sulfonated Acids and Esters, J. Amer. Oil. Chem. Soc.,vol. 31, p. 13, 1955. Library of Congress TP 1.05 (4 pages).

The Condensed Chemical Dictionary, 7th edition, Rose, Reinhold, NewYork, 1967, pp. 874, 867, 868.

LEON D. ROSDOL, Primary Examiner.

S. E. DARDEN, Assistant Examiner.

gg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,413,221 DatedNovember 26, 1968 Patent No.

Inventor) Ernst Gotte, Werner Stein and Herbert Weiss It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

' Column 10, line 70, cancel "in the alkyl radical"; line 71, after"atoms" and before the period insert --in the alkyl radica1 SIGNED ANDSEALED EB3 4979 (SEAL) I Am mum: E. sum. 33. EdwardMFletchmIGommissioner of Patents Attesting Officer

